JPH11271930A - Photographic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To lower the Dmin increasing tendency of a photosensitive layer located near by incorporating a specified group or its tautomer on the ring of a compound and inhibiting it from reaction with the oxidation product of a developing agent. SOLUTION: The photographic element comprises a nonphotosensitive silver halide emulsion layer containing atomic silver metal and the heterocyclic thiol compound having C log P of at least 2.0 but <12.0, and the ring of this compound has a -N=C-S-H group or its tautomer, and inhibited from reaction with the oxidation product of a developing agent. The photographic element comprises a red-sensitive silver halide emulsion layer containing a nondiffusible cyan coupler and a green-sensitive silver halide emulsion layer containing a nondiffusible magenta coupler and a blue-sensitive silver halide emulsion layer containing a nondiffusible yellow coupler and the nonphotosensitive layer containing both of an atomic silver metal and the heterocyclic thiol compound having a total C log P of at least >=2.0 but <12.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to color photographic elements containing elemental silver and a heterocyclic thiol compound in the non-photosensitive layer.

[0002]

BACKGROUND OF THE INVENTION It has been a long-standing goal of silver halide color photographic materials to form images of a subject in a precise manner, both in terms of color and image structural properties (eg, graininess and sharpness). It is well known that the perceived sharpness of a photographic image can be reduced by halation effects (ie, reflection within the light-capturing element and subsequent scattering of light), particularly reflection from the support. It is also well known to reduce the light reflection by using an antihalation layer between the support of the film and the sensitizing layer. To be effective, the antihalation layer contains a substance that absorbs light and prevents reflection. Generally, it is highly desirable that the light absorbing material be completely removed from the film element after development (otherwise it will be colorless) to avoid increasing background density.

A well-known type of light-absorbing material suitable for use in an antihalation layer is colloidal or finely divided elemental silver or metallic silver (also called "gray" silver). This type of silver metal is filamentous and in such form, absorbs light throughout the visible spectrum, which appears gray or black. It is generally easily removed from the element by conventional bleaching and fixing steps used to remove imaging silver from the film element. This silver metal is not photosensitive and does not contribute to image formation. TH James's The Theor
y of the Photographic Process, 4th edition, p.579, U.S. Patent No. 3,434,839, JP-A-09-06.
No. 7122 and YJ Zahng et al., Chin. Chem. Let.
t. 7 ( 7), 687-690 (1996).

Another use of colloidal or microfractionated elemental or metallic silver is as a blue light absorbing filter. This form (commonly referred to as Kelly-Lee silver) differs from "grey" silver in that the form is spherical. F. Evva, J. Signalaufzeichnungmateria
lien, 4 ( 1), 43-60 (1976) and G. Frens, Kolloid-Z.
See Z. Polym, 233 ( 1-2), 922-9 (1969). This material is generally located in a non-image-forming layer (commonly referred to as a "yellow filter layer") that is further from the light source than the blue-sensitive emulsion layer or "directly under" the blue-sensitive emulsion layer. The function of this layer is to absorb any blue light not captured by the blue sensitized layer, so that the underlying green and red sensitized emulsion layers (which have inherently a little blue sensitivity) are exposed to blue light. Prevents unwanted exposure.

A problem associated with using elemental silver for both the antihalation layer and the yellow filter layer is the undesirable increase in fog of nearby imaging layers. Upon development, silver ions are released from the imaging layer and / or become soluble. These silver ions can migrate to the non-photosensitive layer where elemental silver is present.
Silver can serve as a nucleus that reduces moving silver ions to metallic silver and simultaneously oxidizes the developing agent to the oxidized developing agent. This process is called dissolution physical development (T.
See H. James, ibid, Chapter 13), non-image-like. Oxidized developing agent may diffuse back from the antihalation layer back to a nearby imaging layer, where it can react with the coupler present to form a dye non-imagewise. This process is often very sensitive and can result in variations in Dmin during photofinishing.

Another problem with using elemental silver in non-imaging layers is that these layers can absorb inhibitor fragments and other silver absorbing materials. This reduces the effective concentration of free species in the image forming layer. It may also occur that the diffusion of such species through the layer containing elemental silver is limited.

It is also known to alter the dissolution physical development which requires elemental silver by using additives. For example, UK Patent Application Publication No. 2280276, U.S. Pat. No. 3,647,439, German Patent 1949418, East German Patent 2006 9
The 1/6 specification and JP-A-3-138639 describe various classes of substances (including various types of thiols) useful for controlling the properties of elemental silver. In particular, in US Pat. No. 3,647,439 and East German Patent 2006 91/6,
The use of various types of heterocyclic thiols for non-photosensitive layers is described. However, in these documents, the substance is water-soluble and, of all the examples of heterocyclic thiols shown, the average ClogP is 1.66 and the maximum Cl
ogP is 3.18 (German Patent 2006 91/6)
Compound 11) of Table II in the description. Such a water-soluble substance diffuses into the image forming layer, where the development is suppressed and the sensitivity may be lowered, which is not preferable.

[0008] Dissolution physical development may be facilitated by substances which form soluble silver salts. In particular, substances that release low molecular weight water soluble thiols (used as bleach accelerators) can increase the amount of dissolved physical development. Couplers that release such thiols are known as bleach accelerator releasing couplers. For example, EP 193389, U.S. Pat. No. 4,861,701
Nos. 4,959,299 and 4,912,0
Nos. 24, 5,300,406 and 5,358,
See No. 828, each specification. Imagewise means that do not require direct coupling with the oxidized developing agent (e.g.,
U.S. Pat. No. 4,684,604) or non-image-like means (U.S. Pat. Nos. 4,923,784, 4,8).
Nos. 65,956 and 5,019,492)
It is also possible to release similar bleaching accelerators from substances other than couplers. Thus, when a bleaching accelerator is also present, an increase in Dmin in the image forming layer near the non-image forming layer containing colloidal silver is a particular problem.

[0009] Substituted mercaptotetrazole is generally known in the art as both an inhibitor fragment and an anti-capri agent. In the case of inhibitor fragments, they are attached to the coupling moiety through a sulfur or nitrogen atom and do not interact with silver until coupling occurs and the sulfur atom is released (US Pat. No. 3,227,554). Issue specifications and CR Barr etc.
Sci. Eng., 74 , 214 (1969)). As part of the DIR, mercaptotetrazole has no free -SH or -NH groups. In general, it is preferred that the mercaptotetrazole released from the DIR be partially water-soluble so that it can freely diffuse into other layers to produce an interimage.

As antifoggants, these materials are generally at least partially water-soluble or soluble in water-miscible solvents (eg, methanol) and added directly to the silver emulsion before coating the film. Or added directly to the developer. Using various soluble mercaptotetrazole as an antifoggant,
For example, Research Disclosure
sure), June 1984, pp. 274-278; U.S. Pat. No. 4,955.
2,485, 5,362,620, 5,24
4,779, 4,963,475, 3,26
6,897, each specification; Belgian Patent No. 747,628
Patent Specification; British Patent No. 1,275,701; Japanese Patent Application JP-05-313282; European Patent Publication 454149; Japanese Patent Application JP-
02-207248; EP 50
9519 and 337370.

[0011] EP 0 369 486 describes:
2-mercapto-benzoxazole for use in combination with the fine silver halide emulsion in the protective layer,-
Benzothiazole and -benzodiazole are described, wherein the sensitivity of the fine silver halide emulsion is one or more exposure units lower than that of the lowest sensitivity silver halide emulsion present in another layer. JP-A-03-163435 discloses the use of a mercaptooxadiazole derivative together with a virtually light-insensitive silver halide emulsion. In both of these references, the silver halide emulsion is not elemental silver.

[0012]

The problem to be solved is to provide a photographic element having a non-photosensitive layer containing elemental silver, which has a reduced tendency for the Dmin of the nearby light-sensitive layer to increase.

[0013]

The present invention comprises a light-insensitive silver halide emulsion layer containing elemental silver and a heterocyclic thiol compound having a ClogP of at least 2.0 but less than 12.0. Wherein the ring system of the compound comprises a —N ＝ C—S—H group or a tautomer thereof, and does not react with the oxidized developing agent. The present invention lowers the Dmin value of the image forming layer.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The photographic elements of the present invention are generally those described under "Means for Solving the Problems". This element typically comprises at least one red-sensitive silver halide emulsion layer containing at least one non-diffusible cyan coupler, at least one green-sensitive silver halide emulsion containing at least one non-diffusible magenta coupler. And at least one blue-sensitive silver halide emulsion layer containing at least one non-diffusing yellow coupler, and silver metal in elemental form and a total ClogP of Formula I of at least 2.0 but less than 12.0. It relates to a light-sensitive color photographic element having at least one light-insensitive layer containing both certain heterocyclic thiols.

[0015]

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In the formula I, I, W, Y and Z represent the nitrogen, oxygen, and hydrogen required to complete a 5- or 6-membered heterocyclic ring system.
It can be any combination of sulfur and carbon atoms. n is 1 or 2. Q is a ballast moiety that is permanently attached to a portion of the heterocyclic system such that the compound has a total ClogP of at least 2.0 but less than 12.0. The bond between the W, Y and Z atoms (indicated by the dotted line) is a single or double bond required to complete the ring. Any carbon atom present in the ring may be a hydrogen atom or another substituent (eg, a nitrogen group such as an alkyl group, a phenyl group, an ether group, a thioether group, an amino, aminocarbonyl or aminosulfonyl, an oxygen, a sulfoxide group, a sulfone) Groups, halides such as chloro or bromo, cyano groups, nitro groups, keto, carboxylic acids, carboxylate esters, carbonyl groups such as carbamoyl) or other substituents as generally described below. . These substituents can combine with each other to form an additional ring system, and the benzo or naphtho ring can form a ring to form a heterocyclic nucleus. The compounds of formula I can be written in two tautomeric forms (-N = CSH form or -NH-C = S form). Because these two forms are chemically identical and equivalent, the compounds of the present invention are described only in the -N = CSH form.

Some examples of ring systems of the formula I according to the invention are mercaptotetrazole, mercapto-1,2,3 triazole, mercaptotetraazaindene, mercaptopurine, mercaptopyrazolotriazole, thiopyrimidine, oxazolididine-2-thione. Thiazoline, cyclic thiourea, pseudothiohydantoin, 2-thioimidazolidin, mercaptoimidazole, mercaptooxazole, mercaptooxadiazole, mercaptothiadiazole and the like. Most preferred ring systems for use in the present invention are mercaptotetrazole, mercaptooxadiazole and mercaptothiadiazole.

In the compound of formula I, Q is a ballast group that provides sufficient bulk, molecular weight and oil solubility to meet specified ClogP requirements, and the compound cannot substantially diffuse into other layers. Preferred Q groups include substituted or unsubstituted alkyl or aryl groups having 8 to 48 carbon atoms, alkyloxy or aryloxy groups, carbonamido (-NRC
O-) or carbamoyl (-CONR-) groups, sulfonamide (-NRSO ₂ - contains) or a sulfamoyl group (-SO ₂ NR-) or alkylthiol or aryl thiol group. Representative additional substituents on such groups include alkyl, aryl, alkoxy,
Aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamide, carbamoyl, alkylsulfonyl, arylsulfonyl, sulfonamide, and sulfamoyl groups, and their substitution The groups generally have 1 to 42 carbon atoms. Such substituents may be further substituted. The substances of formula I are not couplers and do not react with oxidized developing agents. Such reactions adversely affect color, image formation efficiency, and the like.

An important feature of the heterocyclic thiols of formula I is that
The oil / water partition coefficient. Oil / water partition coefficient is Medchem
3.54 Calculated using the software program, Clo
This value can be predicted as gP (calculated log distribution coefficient). Medchem version 3.54 is available for Medicinal Chem
istry Project, a software program created by Pomona College, Pomona California. To obtain the desired reduction in Dmin and fog of the nearby imaging layers,
It has been found that the water solubility cannot be so low that this material cannot effectively interact with the silver surface. Furthermore, a high ClogP makes it impossible to remove the corresponding silver salt in the bleaching and fixing steps of the process. Thus, it is preferred that the overall ClogP of the heterocyclic thiol of Formula I does not exceed 12.0, and most preferably that ClogP does not exceed 6.0. However, it has also been found that the solubility in water cannot be so high that this material diffuses from the layer containing elemental silver to the adjacent imaging layer, causing photosensitivity loss. Accordingly, it is necessary that the ClogP of the heterocyclic thiol of Formula I be at least 2.0, more preferably at least 3.0 or most preferably 3.5.

In general, the heterocyclic thio of formula I to silver
Mole ratio of at least 0.1, more preferably
At least 1.0, but less than 100,
Preferably, it is less than 50. Heterocyclic thiol of formula I
In the protonated form as shown or the corresponding
Introduce to the non-photosensitive layer as one of the protonated salts
Can be A preferred counter ion is sodium (Na
⁺) Or potassium (K⁺) Or tetramethylammo
Nium (N (CH_Three )_Four ⁺), Tetraethylammonium
(N (C_Two H _Five )_Four ⁺) Or cyclohexylane
Monium (C₆ H₁₃NH_Three ⁺) And other ammonium cations
It becomes.

Examples of heterocyclic thiols useful in the present invention are shown below, together with the ClogP values listed in parentheses:

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[0022]

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[0023]

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The heterocyclic thiols of the present invention are conveniently used with compounds commonly used as scavengers for oxidized developing agents. Such scavengers are available from Research Disclosure as described below.
Disclosure), for example, phenol derivatives and hydroquinone derivatives (for example, 2,4-di-t)
-Octyl-hydroquinone).

The substance of the present invention may be added to the solution containing silver before coating, or may be mixed with silver immediately before or during coating. In either case, additional components such as couplers, doctors, surfactants, hardeners and other materials typically present in such solutions can be present at the same time. The substances according to the invention are not water-soluble and cannot be added directly to this solution. If dissolved (more preferably as a dispersion) in an organic water-miscible solution (eg, methanol, acetone, etc.), it can be added directly. The dispersion introduces the substance in a stable, finely divided state into a hydrophobic organic solvent which is stabilized with a suitable surfactant and a surfactant, usually in combination with a binder or matrix such as gelatin. The dispersion can contain one or more permanent coupler solvents that dissolve the substance and maintain it in a liquid state. Examples of suitable permanent coupler solvents are tricresyl phosphate, N, N-diethyllauramide, N, N
N′-dibutyllauramide, p-dodecylphenol,
Dibutyl phthalate, di-n-butyl sebacate, N-
n-butylacetanilide, 9-octadec-ene-1
-Ol, trioctylamine and 2-ethylhexyl phosphate.

The dispersion may initially require an auxiliary coupler solvent to dissolve the components, but is subsequently removed (usually by evaporation or additional washing with water). Examples of suitable co-solvents are ethyl acetate, cyclohexanone and 2-
(2-butoxyethoxy) ethyl acetate. Also, a polymeric material can be added to stabilize the dispersion to form a stable latex. Examples of suitable polymers for this application typically have water solubilizing groups or
It has a highly hydrophilic part. Examples of suitable dispersants or surfactants are Alkanol XC or saponins. The material of the present invention may be dispersed as a mixture with another component of the system, such as a coupler or an oxidized developing agent scavenger, such that both are in the same oil droplet.

Unless otherwise noted throughout this specification,
When a substituent has a substitutable hydrogen, any group (s) described herein may be used, provided that it not only includes unsubstituted forms of the substituent, but also does not destroy the properties required for photographic utility. ) Are intended to include the further substituted forms. Suitable substituents can be halogen or can be attached to the residue of the molecule by a carbon, silicon, oxygen, nitrogen, phosphorus, or sulfur atom.

Suitable substituents are, for example, halogens such as chlorine, bromine or fluorine; nitro; hydroxyl; cyano; carboxyl; Alkyl including alkyl (eg, methyl, trifluoromethyl, ethyl, t-butyl, 3- (2,4-di-
t-pentylphenoxy) propyl and tetradecyl); alkenyl such as ethylene and 2-butene; methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2- (2,
4-di-t-pentylphenoxy) ethoxy, and 2-
Alkoxy such as dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl, 2,4,6-trimethylphenyl, naphthyl; phenoxy,
Aryloxy such as -methylphenoxy, α- or β-naphthyloxy, and 4-tolyloxy; acetamido, benzamide, butylamide, tetradecaneamide, α- (2,4-di-t-pentyl-phenoxy) acetamide, α- (2,4-di-t-pentylphenoxy) butyramide, α- (3-pentadecylphenoxy) -hexaneamide, α- (4-hydroxy-3
-T-butylphenoxy) -tetradecaneamide, 2-
Oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrolin-1-yl, N-methyltetradecaneamide, N-succinimide, N-phthalimide, 2,
5-dioxo-1-oxazolidinyl, 3-dodecyl-
2,5-dioxo-1-imidazolyl, and N-acetyl-N-dodecylamino, ethoxycarbonylamino,
Phenoxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino, 2,
4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 2,5- (di-t-pentylphenyl) carbonylamino, p-dodecylphenylcarbonylamino, p-tolylcarbonylamino, N-methylureido, N, N-dimethylureido, N-methyl-
N-dodecyl ureide, N-hexadecyl ureide,
N, N-dioctadecylureide, N, N-dioctyl-N′-ethylureide, N-phenylureide,
N-diphenylureide, N-phenyl-Np-tolylureide, N- (m-hexadecylphenyl) ureide, N, N- (2,5-di-t-pentylphenyl)-
Carbonamides such as N'-ethylureido and t-butylcarbonamide;

Such as methylsulfonamide, benzenesulfonamide, p-tolylsulfonamide, p-dodecylbenzenesulfonamide, N-methyltetradecylsulfonamide, N, N-dipropylsulfamoylamino, and hexadecylsulfonamide Sulfonamide; N-methylsulfamoyl, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-hexadecylsulfamoyl, N, N-dimethylsulfamoyl, N- [3- (dodecyl Oxy) propyl] sulfamoyl, N- [4- (2,4-di-t-pentylphenoxy) butyl] sulfamoyl, N-methyl-N-tetradecylsulfamoyl, and sulfamoyl such as N-dodecylsulfamoyl N-methylcarbamoyl, N, N-dibutyl Rubamoiru, N- octadecylcarbamoyl, N- [4-(2,4-di -t- pentylphenoxy) butyl] carbamoyl, N- methyl -N-
Carbamoyl, such as tetradecylcarbamoyl and N, N-dioctylcarbamoyl; acetyl, (2,4
-Di-t-amylphenoxy) acetyl, phenoxycarbonyl, p-dodecyloxyphenoxycarbonyl,
Methoxycarbonyl, butoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 3-pentadecyloxycarbonyl,
And acyl such as dodecyloxycarbonyl; methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, 2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl, 2- Sulfonyl such as ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl, phenylsulfonyl, 4-nonylphenylsulfonyl, and p-tolylsulfonyl; sulfonyloxy such as dodecylsulfonyloxy and hexadecylsulfonyloxy;

Sulfinyl such as methylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 4-nonylphenylsulfinyl and p-tolylsulfinyl; ethylthio, octylthio, benzylthio, tetradecylthio, 2-
(2,4-di-t-pentylphenoxy) ethylthio,
Thio such as phenylthio, 2-butoxy-5-t-octylphenylthio, and p-tolylthio; acetyloxy, benzoyloxy, octadecanoyloxy, p
Acyloxy such as -dodecylamidobenzoyloxy, N-phenylcarbamoyloxy, N-ethylcarbamoyloxy and cyclohexylcarbonyloxy; amines such as phenylanilino, 2-chloroanilino, diethylamine, dodecylamine; 1- (N-
Phenylimido) iminos such as ethyl, N-succinimide or 3-benzylhydantoinyl; phosphates such as dimethylphosphate and ethylbutylphosphate; phosphites such as diethyl and dihexylphosphite; 2-furyl, 2-thienyl; Each of 3 to 3 which may be substituted and is composed of carbon and at least one heteroatom selected from the group consisting of oxygen, nitrogen and sulfur, such as 2-benzimidazolyloxy or 2-benzothiazolyl.
A heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group having a 7-membered heterocyclic ring; a quaternary ammonium such as triethylammonium; and a silyloxy such as trimethylsilyloxy.

If desired, the substituents themselves may be further substituted one or more times with the described substituents. One skilled in the art can prune the particular substituents used to obtain the desired photographic properties for the particular application, including, for example, hydrophobic groups, solubilizing groups, blocking groups, releasing or releasable groups. Etc. are included. Generally, the above groups and their substituents will have up to 48 carbon atoms, typically 1 to 3 carbon atoms.
6, which may include those usually having less than 24 carbon atoms, although higher numbers of carbon atoms are possible depending on the particular substituents selected.

The substances of the present invention can be used in any of the ways and in any of the combinations known in the art. Generally, the materials of this invention are incorporated into a silver halide emulsion and the emulsion coated to form a photographic element. Alternatively, otherwise the substances of the present invention can be incorporated in the vicinity of the silver halide emulsion layer, where upon development these substances react reactively with development products such as oxidized color developing agents. Combine. Accordingly, as used herein,
The term "combines" means that the compound is in the silver halide emulsion layer or is in close proximity so that it can react with the silver halide development product during development.

To control the migration of various components, it is desirable to include high molecular weight hydrophobic substances or high molecular weight or polymer backbones containing "ballast" groups in the molecule. Representative ballast groups include substituted or unsubstituted alkyl or aryl groups having 8 to 48 carbon atoms. Representative substituents on those groups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl,
Includes aryloxycarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamide, carbamoyl, alkylsulfonyl, arylsulfonyl, sulfonamide, and sulfamoyl groups, the substituents of which generally have 1-42 carbon atoms . Further, such a substituent may be further substituted.

The photographic elements can be single color elements or multicolor elements. Multicolor elements have image dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers (including the image-forming units) in the element can be arranged in various orders as known in the art. In another format, emulsions sensitive to each of the three primary regions of the spectrum can be arranged as a single segmented layer.

A typical multicolor photographic element of the present invention comprises a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler; Magenta dye image-forming units comprising at least one green-sensitive silver halide emulsion layer having associated therewith a magenta dye-forming coupler and at least one blue-sensitive halide having associated therewith at least one yellow dye-forming coupler A support having a yellow dye image-forming unit comprising a silver emulsion layer. This element consists of a filter layer, an intermediate layer,
It can have additional layers such as overcoat layers, undercoat layers, and the like.

[0036] If desired, the photographic element, Risachide
Office closures, November 1992, Item 34390 (UK, Kenneth Mason in the Hampshire P0107DQ Emsworth 12a North Street, Dudley Annex
Publications, Inc.) and Invention Association Published Technical Report No. 94-6
No. 023 (issued March 15, 1994, available from the JPO), the contents of which are incorporated herein by reference. It can be used in combination with a layer. When it is desirable to use the materials of the present invention in small films, a suitable embodiment is described in Research Disclosure , June 1994, Item 36230.

In the following description of materials suitable for use in the emulsions and elements of the present invention, reference is made to Research Disclosure , September 1996, Item 38957 (hereinafter "Research Disclosure"), available as described above. refer. The contents of Research Disclosure (including the patents and publications mentioned therein) are incorporated herein by reference, and the sections referred to below are Research Disclosure sections.

Unless otherwise specified, silver halide emulsion-containing elements used in this invention are dictated by the type of processing instruction specified for the element (ie, color negative, reversal or direct positive processing). It can be either negative or positive. Suitable emulsions and their preparation, as well as methods of chemical and spectral sensitization, are described in Sections IV. UV dye, optical brightener, antifoggant,
Various additives such as stabilizers, light absorbing and scattering substances, and physical property improving additives such as hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections II and VI-VIII. Are listed. Color materials are described in Sections X-XIII. Suitable methods for introducing couplers and dyes (including dispersions in organic solvents) are described in Section X (E). Scan facilitation is described in Section XIV. Supports, exposure, development systems, and processing methods and agents are described in Sections XV-XX. The information contained in the above-mentioned Research Disclosure ,, Item 36544, September 1994, Risachide
Disclosure , Item 38957, updated in September 1996. Certain preferred photographic elements and processing steps are described in Research Disclosure , Item 37038, February 1995.

[0039] Coupling leaving groups are well known in the art. Such groups can determine the chemical equivalent (ie, 2 or 4 equivalents) of the coupler (ie, alter the reactivity of the coupler). After such groups are released from the coupler, the coupler is coated by performing functions such as dye formation, dye hue adjustment, development promotion or suppression, bleach promotion or suppression, electron transfer promotion, and color correction. Layers or other layers in the photographic recording material can be advantageously influenced.

The presence of hydrogen at the coupling site gives a 4-equivalent coupler, and the presence of another coupling-off group usually gives a 2-equivalent coupler. Representative types of such coupling-off groups include, for example,
Chloro, alkoxy, aryloxy, heterooxy,
Heterocyclic groups such as sulfonyloxy, acyloxy, acyl, oxazolidinyl or hydantoinyl, sulfonamide, mercaptotetrazole, benzothiazole, mercaptopropionic acid, phosphonyloxy, arylthio and arylazo. These coupling-off groups are described in the art, for example, in U.S. Patent Nos. 2,455,169, 3,227,551.
Nos. 3,432,521 and 3,476,563
No. 3,617,291, 3,880,661
Nos. 4,052,212 and 4,134,766
And UK Patent and Application Publication No. 1,466.
728, 1,531,927, 1,533,0
Nos. 39, 2,006,755A and 2,017,
No. 704A, which is incorporated herein by reference.

"Farbkuppler-eine Literature Ubersich
t ", published by Agfa Mitteilungen, Volume III, pp. 156-175 (1961), and U.S. Pat. Nos. 2,367,531, 2,423,730, 2,474,293, and 2,772. Nos. 162, 2,895,826, 3,002,836, 3,034,892, 3,041,236, 4,333,999, and 4,746,602 Nos. 4,753,871, 4,770,988, 4,775,616, 4,818,667, 4,818,672, 4,822,729, and 4,839,267, 4,840,883, 4,849,328, 4,865,961, 4,873,183, 4,883,746 and 4, Nos. 900,656, 4,904,575, 4,916,051, 4, 21,783, 4,923,791, 4,950,585, 4,971,898, 4,990,436, 4,996,139, 5,008, Nos. 180, 5,015,565, 5,011,765, 5,011,766, 5,017,467, 5,045,442, and 5,051,347 No. 5,061,613, No. 5,071,737, No. 5,075,207, No. 5,091,297, No. 5,094,938, No. 5,104,783, No. 5,178,993, 5,813,729, 5,187,057, 5,192,651, 5,200,305, 5,202,224, 5, Nos. 206,130, 5,208,141, 5,210,011, 5,215,871, 5,223,386, 5,227,287, 5,256,526, 5,258,270, 5,272,051, and 5, 306,610, 5,326,682, 5,366,856, 5,378,596, 5,380,638, 5,382,502, 5,384 Nos. 236, 5,397,691, 5,415,990, 5,434,034, and 5,441,863, European Patent No. 02466.
No. 16, No. 0250201, No. 0271323, No. 0295632, No. 0307927, No. 03331
No. 85, No. 0378889, No. 0389817, No. 0487111, No. 0488248, No. 05390
No. 34, No. 0545300, No. 0556700, No. 0556777, No. 0556858, No. 05699
No. 79, No. 0608133, No. 0636936, No. 0651286, No. 0690344, German Patent Publication Nos. 4,026,903, 3,624,777 and 3,823,049. Image dye-forming couplers, such as couplers that form cyan dyes upon reaction with oxidized color developing agents, as described in specific patent specifications and publications, can be included in the elements of the present invention. Typical such couplers are phenols,
Naphthols and pyrazoloazoles.

Couplers that form magenta dyes upon reaction with oxidized color developing agents are described in Farbkuppler-eine L.
iterature Ubersicht, published by Agfa Mitteilungen, No.
III, pages 126-156 (1961), and U.S. Pat.
11,082, 2,369,489, 2,34
No. 3,703, No. 2,600,788, No. 2,90
8,573, 3,062,653, 3,15
2,896, 3,519,429, 3,75
No. 8,309, No. 3,935,015, No. 4,54
0,654, 4,745,052, 4,76
2,775, 4,791,052, 4,81
2,576, 4,835,094 and 4,84
Nos. 0,877, 4,845,022 and 4,85
3,319, 4,868,099, 4,86
5,960, 4,871,652, 4,87
6,182, 4,892,805, 4,90
0,657, 4,910,124, 4,91
4,013, 4,921,968, 4,92
9,540, 4,933,465 and 4,94
No. 2,116, No. 4,942,117, No. 4,94
2,118, 4,959,480, 4,96
8,594, 4,988,614, 4,99
2,361, 5,002,864, 5,02
1,325, 5,066,575, 5,06
Nos. 8,171, 5,071,739, 5,10
0,772, 5,110,942, 5,11
6,990, 5,118,812, 5,13
4,059, 5,155,016, 5,18
3,728, 5,234,805, 5,23
5,058, 5,250,400, 5,25
4,446, 5,262,292, 5,30
0,407, 5,302,496, 5,33
6,593, 5,350,667, 5,39
5,968, 5,354,826, 5,35
8,829, 5,368,998, 5,37
8,587, 5,409,808, 5,41
No. 1,841, No. 5,418,123, No. 5,42
No. 4,179, European Patent Nos. 0257854 and 028
No. 4240, No. 0341204, No. 347, 235
Nos. 365, 252, 0422595, 04
No. 28899, No. 0428902, No. 0459331
Nos. 0467327, 0476949, 04
87081, 0489333, 0512304
Nos. 0515128, 0534703, 05
No. 54778, No. 0558145, No. 0571959
No. 0583833, 0583834, 05
No. 84793, No. 602748, No. 0602749
Nos. 0605918, 0622672 and 06
No. 22683, No. 0629912, No. 064684
1, 0656561, 0660177, 06
No. 86872, WO90 / 10253, WO92 / 0
No. 9010, WO92 / 10788, WO92 / 12
No. 464, WO93 / 01523, WO93 / 023
No. 92, WO93 / 02393, WO93 / 0753
No. 4, UK Patent Application No. 2,244,053, Japanese Patent Application No. 03192-350, German Patent Publication 3,
Representative patent specifications and publications, such as 624,103, 3,912,265 and DE-A-400806. Typical such couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles which form a magenta dye upon reaction with an oxidized color developing agent.

Couplers that produce yellow dye upon reaction with oxidized color developing agent are described in Farbkuppler-eine L.
iterature Ubersicht, published by Agfa Mitteilungen, No.
III, pages 112-126 (1961), and U.S. Pat.
98,443, 2,407,210, 2,87
5,057, 3,048,194, 3,26
5,506, 3,447,928, 4,02
No. 2,620, No. 4,443,536, No. 4,75
8,501, 4,791,050, 4,82
4,771 and 4,824,773, 4,85
5,222, 4,978,605, 4,99
2,360, 4,994,361, 5,02
1,333, 5,053,325, 5,06
6,574, 5,066,576, 5,10
0,773, 5,118,599, 5,14
3,823, 5,187,055, 5,19
0,848, 5,213,958, 5,21
5,877, 5,215,878, 5,21
7,857, 5,219,716, 5,23
8,803, 5,283,166, 5,29
No. 4,531, No. 5,306,609, No. 5,32
8,818, 5,336,591, 5,33
8,654, 5,358,835, 5,35
8,838, 5,360,713, 5,36
2,617, 5,382,506, 5,38
9,504, 5,399,474, 5,40
5,737, 5,411,848, 5,42
No. 7,898, European Patent Nos. 0327776 and 029.
Nos. 6793, 0365282 and 0379309
Nos. 0415375, 0437818, 04
No. 47969, No. 0542463, No. 0568037
Nos. 0568196, 0568777, 05
Nos. 70006, 0573761, 0608956
Nos. 0608957 and 0628865, and the like. Such couplers are typically open chain ketomethylene compounds.

Couplers which form colorless products upon reaction with oxidized color developing agents are described in GB 861,13.
No. 8, U.S. Pat. Nos. 3,632,345 and 3,92.
8,041, 3,958,993 and 3,96
It is described in typical patent specifications such as 1,959. Typical such couplers are cyclic carbonyl-containing compounds that form colorless products upon reaction with an oxidized color developing agent.

Couplers capable of forming a black dye upon reaction with a color developing agent are described in US Pat. Nos. 1,939,231, 2,181,944, 2,333,106 and 4,126,461. Description, German Patent Publication No. 2,
No. 644,194 and 2,650,764. Typically, such couplers are resorcinols or m-aminophenols that form a black or neutral product upon reaction with an oxidized color developing agent.

In addition to the above, so-called "universal" or "washout" couplers can be used. These couplers do not contribute to image dye formation. Thus, for example, naphthol having unsubstituted carbamoyl or naphthol substituted at the 2- or 3-position with a low molecular weight substituent can be used. Couplers of this type are described, for example, in U.S. Pat. Nos. 5,026,628, 5,151,343 and 5,234,800.

US Pat. Nos. 4,301,235;
It is also useful to use coupler combinations that can include any of the known ballast or coupling-off groups as described in US Pat. Nos. 853,319 and 4,351,897. The coupler can have a solubilizing group as described in U.S. Pat. No. 4,482,629. Further, couplers are disclosed in EP 213,490, JP-A-58-172.
No. 647, U.S. Pat.
70,191, 4,273,861, German Patents 2,706,117 and 2,643,965
As described in U.S. Patent No. 1,530,272 and Japanese Patent Application No. 58-113935, together with a "wrong" colored coupler (e.g. (To adjust the level of interlayer compensation), and in color negative applications, can be used with a masking coupler. If necessary, the masking coupler can be shifted or blocked.

The photographic element can be used with materials that release "photographically useful groups" (PUGs) to enhance or improve the bleaching or fixing process steps to improve image quality. As described in the literature, these bleach releasers may or may not be couplers. Bleaching accelerator releasing type as described in European Patent Nos. 193389, 301377, U.S. Pat. Nos. 4,163,669, 4,865,956 and 4,923,784. Couplers can be useful.
Further, a composition relating to a nucleating agent, a development accelerator or a precursor thereof (British Patent Nos. 2,097,140 and 2,097,140)
131,188); Electron transfer agents (U.S. Pat. Nos. 4,859,578 and 4,912,025); Antifogging of hydroquinone, aminophenol, amine, derivatives of gallic acid, etc. It is also conceivable to use catechol; ascorbic acid; hydrazide; sulfonamidophenol; and non-color-forming couplers.

Further, the material of the present invention can be used as a colloidal silver sol or a yellow, cyan and / or magenta filter dye (as an oil-in-water dispersion, a latex dispersion,
(As a solid particle dispersion). In addition, the photographic materials of the present invention may be used with "smearing" couplers (e.g., U.S. Pat. No. 4,366,237, EP 96,570, U.S. Pat. Nos. 4,420,556 and 4,104). 543,323). The composition may be blocked or coated in a protected form, for example, as described in Japanese Patent Application No. 61-258249 or US Pat. No. 5,019,492.

The materials of the present invention can further contain a PUG releasing image improving compound such as a "development inhibitor releasing" compound (DIR). Useful DIRs associated with the compositions of the present invention are known in the art, examples of which are described in US Pat. No. 3,137,578;
3,148,022, 3,148,062, 3,227,554, 3,384,657, 3,379,529, 3,615,506, and 3 Nos. 3,617,291, 3,620,746, 3,701,783, 3,733,201, 4,049,455, 4,095,984, 4,126. No. 4,459,886, No. 4,150,228, No. 4,211,562, No. 4,248,962, No. 4,259,437, No. 4,362,878. Nos. 4,409,323, 4,477,563, 4,782,012, 4,962,018, 4,500,634, 4,579,816, 4,607,004, 4,618,571, 4,678,73 Nos. 4,746,600, 4,746,601, 4,791,049, 4,857,447, 4,865,959, 4,880,342, 4,886,736, 4,937,179, 4,946,767, 4,948,716, 4,952,485, 4,956,269, and 4 , 959,299, 4,966,835 and 4,985,336, and Patent Gazettes British Patent Nos. 1,560,240, 2,007,662, and 2,032. Nos. 914 and 2,099,167, and German Patent Nos. 2,842,063 and 2,937,12.
No. 7, 3,636,824 and 3,644,4
No. 16 and EP-A-272,573.
Nos. 335, 319, 336, 411, 34
6,899, 362,870, 365,252
Nos. 365, 346, 373, 382, 37
No. 6,212, No. 377,463, No. 378,236
Nos. 384,670, 396,486, 40
Nos. 1,612 and 401,613.

Further, such a compound is referred to as “Developer-
Inhibitor-Releasing (DIR) Couplers for Color Pho
tography, CRBarr, JR Thirtle and PWVittumin Ph
Also described in otographic Science and Enginieering , Vol. 13, p. 174 (1969) ( incorporated herein by reference). Generally, a development inhibitor releasing type (D
IR) couplers comprise a coupler component and an inhibitor coupling-off component (IN). Inhibitor releasing couplers
It can be a time-delayed (DIAR coupler) that also includes a timing component or chemical switch that delays the release of the inhibitor. Typical inhibitor components are oxazole, thiazole, diazole, triazole, oxadiazole, thiadiazole, oxathiazole, thitriazole, benzotriazole, tetrazole, benzimidazole, indazole, isoindazole, mercaptotetrazole, selenotetrazole, mercaptobenzothiazole , Selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole,
Mercaptobenzimidazole, selenobenzimidazole, benzodiazole, mercaptooxazole, mercaptothiadiazole, mercaptothiazole, mercaptotriazole, mercaptooxadiazole, mercaptodiazole, mercaptooxathiazole, tellurotetrazole or benzoisodiazole. In a preferred embodiment, the inhibitor component or group is
Selected from:

[0052]

Embedded image

In the formula, R _I represents a straight-chain or branched-chain alkyl group having 1 to about 8 carbon atoms, a benzyl group, a phenyl group, or an alkoxy group; R _II is selected from R _I and -SR _I ; R _III is a linear or branched alkyl group having 1 to about 5 carbon atoms, and m is 1 to 3; And R _IV is hydrogen, halogen, and alkoxy, phenyl and carbonamido groups, —COOR _V and —NHCOOR _V (where R _V is a substituted or unsubstituted alkyl group and a substituted and unsubstituted aryl group Selected).

Although the coupler component contained in the development inhibitor releasing coupler is generally capable of producing an image dye corresponding to the layer in which it is disposed, it may produce different colors as associated with different film layers. it can. It is also useful for the coupler component contained in the development inhibitor releasing coupler to produce a colorless product and / or a product that is washed away from the photographic material during processing (a so-called "universal" coupler).

Compounds such as couplers may release PUG directly upon reaction of the compound during processing or indirectly through a timing or linking group.
The timing group is a group using an intramolecular nucleophilic substitution reaction (US Pat. No. 4,248,962); a group using an electron transfer reaction along a conjugated system (US Pat. No. 4,409,962).
Nos. 323, 4,421,845 and 4,861,
No. 701, Japanese Patent Application No. 57-188035
Nos. 58-98728, 58-209736 and 58-209736); groups which function as couplers or reducing agents after the coupler reaction (U.S. Pat. Nos. 4,438,193 and 4,618, 571 specification); and a group having the above-mentioned features,
Perform a time delayed release of the UG. It is common for the timing group to consist of one of the following formulas:

[0056]

Embedded image

In the formula, IN is an inhibitor component, and Z is a nitro group, a cyano group, an alkylsulfonyl group, a sulfamoyl (—SO ₂ NR ₂ ) group and a sulfonamide (—NRS
Selected from the group consisting of O ₂ R) groups, n is 0 or 1, and R _VI is selected from the group consisting of substituted and unsubstituted alkyl groups and substituted and unsubstituted phenyl groups. The oxygen atom of each timing group is attached to the coupling-off position of each coupler component of the DIAR.

The timing groups or linking groups can also function by electron transfer to a non-conjugated chain. Linking groups are known in the art under various names. They are often referred to as groups that can use a hemiacetal or imino ketanol cleavage reaction, or groups that can use a cleavage reaction by ester hydrolysis (US Pat. No. 4,546,073). . This electron transfer to the unconjugated chain generally results in relatively fast decomposition and the formation of carbon dioxide, formaldehyde, or other low molecular weight by-products. These groups are
European Patent Nos. 4,646,612 and 5,523,451.
No. 4,146,396, JP-A-6
Nos. 0-249148 and 60-249149.

In addition to the compounds of formula II of the present invention, suitable development inhibitor releasing couplers for inclusion in the photosensitive photographic emulsion layer include, but are not limited to, the following:

Embedded image

[0060]

Embedded image

Particularly useful in the present invention are tabular grain silver halide emulsions. Specifically contemplated tabular grain emulsions have more than 50% of the total projected area of the emulsion grains,
A thickness of less than 0.3 μm (0.5 μm for a blue-sensitive emulsion) and an average tabularity (T) of more than 25 (preferably 100
Super). Here, the term “tabularity” is: T = ECD / t ² [where ECD is the average equivalent circular diameter of tabular grains (unit: μm), and t is the average thickness of tabular grains (unit: :
μm)] in the art-recognized usage.

The average effective ECD of a photographic emulsion is up to about 10 μm.
m, but in practice the ECD of the emulsion rarely exceeds about 4 μm. Since both photographic speed and granularity increase with increasing ECD, it is generally preferred to use the smallest tabular grain ECD that is compatible with achieving the intended speed requirements.

Emulsion tabularity increases significantly with decreasing tabular grain thickness. In general, it is preferred that the targeted tabular grain projected area be satisfied by thin (t <0.2 μm) tabular grains. To achieve the lowest level of granularity, it is preferred that the targeted tabular grain projected area be filled with ultrathin (t <0.07 μm) tabular grains. Tabular grain thicknesses are typically about 0.
Up to 02 μm. However, thinner tabular grain thicknesses are also contemplated. For example, U.S. Pat. No. 4,672,027 to Daubendiek et al.
A 3 mol% iodide tabular grain silver bromoiodide emulsion of 7 μm has been reported. Ultrathin tabular grain high chloride emulsions are disclosed in Maskasky U.S. Pat. No. 5,217,858.

As noted above, tabular grains of less than the specified thickness account for at least 50% of the total grain projected area of the emulsion. To maximize the benefits of high tabularity, it is generally preferred that tabular grains satisfying the above thickness criteria account for the conveniently achievable maximum percentage of the total grain projected area of the emulsion. . For example, in a preferred emulsion,
Tabular grains satisfying the above thickness criteria account for at least 70% of the total grain projected area. In the highest performance tabular grain emulsions, tabular grains satisfying the above thickness criteria account for at least 90% of the total grain projected area.

Suitable tabular grain emulsions can be selected from a variety of conventional teachings such as: Research Disclosure, Item 22534, January 1983.
And U.S. Patent Nos. 4,439,520 and 4,41.
4,310, 4,433,048, 4,64
3,966, 4,647,528 and 4,66
5,012, 4,672,027, 4,67
8,745, 4,693,964, 4,71
No. 3,320, No. 4,722,886, No. 4,75
5,456, 4,775,617 and 4,79
7,354, 4,801,522, 4,80
6,461, 4,835,095, 4,85
No. 3,322, No. 4,914,014, No. 4,96
No. 2,015, No. 4,985,350, No. 5,06
1,069 and 5,061,616. Tabular grain emulsions consisting primarily of silver chloride are useful, for example, U.S. Patent Nos. 5,310,635 and 5,320,
938 and 5,356,764.

The emulsion can be a surface-sensitive emulsion, ie, an emulsion that forms a latent image primarily on the surface of the silver halide grains, or the emulsion can be predominantly internal latent within the silver halide grains. An image can be formed. The emulsion can be a negative working emulsion, for example, a surface sensitive emulsion or an unfogged internal latent image forming emulsion, or a positive working emulsion if development is performed using uniform exposure or in the presence of a nucleating agent. It can be an unfogged direct positive emulsion (internal latent image forming type). It is.

Particularly useful in the present invention are tabular grain emulsions. Tabular grain emulsions are those having two parallel major crystal faces and an aspect ratio of at least 2. The term "aspect ratio" refers to the equivalent circular diameter (EC
D) divided by its thickness (t). Tabular grain emulsions are those in which such tabular grains contain at least 50% (preferably at least 70%, optimally at least
(At least 90%). Preferred tabular grain emulsions are those in which the average thickness of the tabular grains is less than 0.3 μm, preferably thin (less than 0.2 μm), and most preferably ultra-thin (less than 0.07 μm). The major faces of the tabular grains can be present on {111} or {100} crystal faces. Average ECD of tabular grain emulsion
It rarely exceeds 10 μm and is generally less than 5 μm.

In the most widely used form, the tabular grain emulsion is a high bromide {111} tabular grain emulsion.
Such emulsions are described in U.S. Pat.
No. 520, U.S. Pat. No. 4,434,226 to Wilgus et al.
No. 4,433,048 to Sugimoto et al.
Skasky U.S. Patent Nos. 4,435,501 and 4,46.
Nos. 3,087 and 4,173,320, Daubendi
ek et al., U.S. Pat.
U.S. Pat. No. 4,656,1 to Sowinski et al.
22, Piggin et al., U.S. Pat. Nos. 5,061,609 and 5,061,616; Tsaur et al., U.S. Pat.
147,771, 5,147,772, 5,1
Nos. 47,773, 5,171,659, and 5,
252,453; U.S. Pat.
720 and 5,334,495; Delton U.S. Patent Nos. 5,310,644; 5,372,927;
And U.S. Patent No. 5,4,460,934 to Wen.
No. 70,698, Fenton et al., U.S. Pat.
No. 60, Eshelman et al., U.S. Pat. Nos. 5,612,175 and 5,614,359, and Irving et al., U.S. Pat. No. 5,667,954.

Ultra-thin high bromide {111} tabular grain emulsions are described in US Pat. No. 4,672,027 to Daubendiek et al.
4,693,964, 5,494,789, 5,503,971 and 5,576,168, An
U.S. Patent No. 5,250,403 to toniades et al., U.S. Patent No. 5,503,970 to Olm et al., U.S. Patent No. 5,582,965 to Deaton et al., and U.S. Patent No. 5,667,955 to Maskasky. This is specifically shown in the specification.

High bromide {100} tabular grain emulsions
US Patent Nos. 4,386,156 and 5,38 to gnot
No. 6,156, which is specifically described. High chloride {111} tabular grain emulsions are described in Wey U.S. Pat.
399,215, U.S. Pat. No. 4,41 to Wey et al.
No. 4,306, Maskasky U.S. Pat.
0,463, 4,713,323, 5,06
1,617, 5,178,997, 5,18
3,732, 5,185,239, 5,39
Nos. 9,478 and 5,411,852, and Maskasky et al., U.S. Patent Nos. 5,176,992 and 5,178,998. Ultra thin high chloride {111} tabular grain emulsions
ky U.S. Patent Nos. 5,271,858 and 5,38.
No. 9,509 is specifically described.

The high chloride {100} tabular grain emulsions
Skasky U.S. Patent Nos. 5,264,337 and 5,29.
2,632, 5,275,930 and 5,39
No. 9,477, House et al., U.S. Pat.
No. 0,938, U.S. Pat. No. 5,311, Brust et al.
U.S. Pat. No. 5,3,798 to Szajewski et al.
No. 56,764; Chang et al., U.S. Pat.
3,904 and 5,663,041, Oyam
U.S. Pat. No. 5,593,821 to ada;
U.S. Pat. Nos. 5,641,620 and 5,655 to Ita et al.
No. 2,088, U.S. Pat.
No. 2,089 and U.S. Pat.
No. 665,530. Ultra thin high chloride {100} tabular grain emulsion
It can be prepared by nucleation in the presence of iodide according to the teachings of the above cited specification of Chang et al.

The emulsion can be a surface-sensitive emulsion, ie, an emulsion that forms a latent image predominantly on the surface of the silver halide grains, or the emulsion can be an internal latent predominantly within the silver halide grains. An image can be formed. The emulsion can be a negative working emulsion, for example, a surface sensitive emulsion or an unfogged internal latent image forming emulsion, or a positive working emulsion if development is performed using uniform exposure or in the presence of a nucleating agent. It can be an unfogged direct positive emulsion (internal latent image forming type). Tabular grain emulsions of the latter type are illustrated in US Pat. No. 4,504,570 to Evans et al.

The photographic element can be exposed to actinic radiation (typically in the visible region of the spectrum) to form a latent image, which can then be processed to form a visible dye image. Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. The oxidized color developing agent then reacts with the coupler to produce a dye.

In the case of negative working silver halide, the processing steps described above produce a negative image. One type of such an element (referred to as a color negative film) is one designed for image capture. Speed (the sensitivity of the element to low light conditions) is usually important for obtaining a sufficient image with such elements. Such elements are generally silver bromoiodide emulsions, for example, the British Journal of Photography Annual
of 1988, pages 191-198, Kodak C-41
Processing can be performed by known color negative processing such as processing. If the color negative film element is to be used to create a cinematographic projection print, East
man Kodak H-24 manual
Processing such as Kodak ECN-2 processing can be used to provide a color negative image on a transparent support. The color negative development time is generally 3 minutes 15 seconds or less, preferably 90 minutes.
Seconds or less, or even 60 seconds or less.

The photographic element of the present invention may be introduced into an exposure structure intended for repeated use, or may be variously named, for example, “single-use camera”, “film with lens”, or “photosensitive material package unit”. It can be introduced into an exposure structure intended for a limited application called.

A reversal element can produce a positive image without optical printing. To provide a positive (reversal) image, the exposed silver halide is developed (but does not produce a dye) prior to development with a non-color developing agent prior to the color development step, and the element is then Uniform fogging allows unexposed silver halide to be developed. Such reversal emulsions are generally known as Kodak E-
It is sold with instructions for processing using color reversal processing such as 6 processing. Alternatively, a positive image can be obtained directly using a positive emulsion.

The above emulsions are generally sold with instructions to be processed using any suitable method, for example, the color negative (Kodak C-41) or reversal (Kodak E-6) process described above. Preferred color developing agents are p-phenylenediamines, for example: 4-amino-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N, N-diethylaniline hydrochloride, 4-amino-3- Methyl-N-ethyl-N- (2-methanesulfonamidoethyl) aniline sesquisulfate hydrate, 4-amino-3-methyl-N-ethyl-N- (2-hydroxyethyl) aniline sulfate,
-Amino-3- (2-methanesulfonamidoethyl)-
N, N-diethylaniline hydrochloride, and 4-amino-N
-Ethyl-N- (2-methoxyethyl) -m-toluidine di-p-toluenesulfonic acid. After development, the usual steps of bleaching, fixing, or bleach-fixing (to remove silver or silver halide), washing, and drying follow.
The contents of all patent applications, patents, and other publications cited herein are hereby incorporated by reference.

[0078]

EXAMPLES Synthesis The compounds of the present invention are readily prepared by conventional techniques. The following method is a preferred synthesis of HT-4.

Embedded image

DL-Methionine methyl ester hydrochloride
(2) Anhydrous methanol (1.5 L) was placed in a 5 L three-necked flask equipped with an addition funnel and a gas outlet leading to a fountain. The methanol was cooled in an ice bath for 15 minutes. Acetyl chloride (790 g, 10.05 mol) was added to H through a fountain.
The Cl was added at a rate that minimized it. After the addition, the solution was stirred for 15 minutes, and DL-methionine (1) (500
g, 3.35 mol) in three portions over 20 minutes.

After all of the solids had dissolved, 2,2-dimethoxypropane (700 g, 6.7 mol) was added over 10 minutes to give a light orange brown solution. After 3 days at room temperature, the solution was evaporated under reduced pressure and the remaining dark red oil was poured into acetone (3 L). The oil was stirred until it solidified. After 30 minutes, the solids were filtered and washed with acetone (2 × 250 mL) to remove most of the colored impurities. This solid was triturated again with acetone (2 L) and refiltered to give a colorless solid. The solid was dried under reduced pressure to yield 513 g. The combined filtrates were evaporated under reduced pressure and the residue was treated in the same manner as above to give 111 g of compound 2. Total yield was 624 g (93%).

Compound 3 Methanol (1.5 L) was added to a 5 L three-necked flask equipped with a mechanical stirrer, thermometer, and reflux condenser. DL- Methionine methyl ester hydrochloride (2) (50
(0 g, 2.5 mol) was added (slow exotherm) and the warm solution was cooled to 15 ° C. in an ice bath. Carbon disulfide (23
(8 g, 3.13 mol) were added all at once. Triethylamine (556 g, 5.51 mol) was added in four portions and the temperature was maintained below 20 ° C. The ice bath was removed and the solution was heated to reflux for 30 minutes. Then, the pale yellow solution was cooled to 10 ° C., and iodomethane (43
6g, 3.00 mol) were added in four portions and the temperature was increased to 3
Maintained below 0 ° C.

After each portion was added to the solution, it was recooled to 15 ° C., and then the next portion was added. After the addition, the ice bath was removed and the solution was stirred for 1 hour. The solution was then evaporated under reduced pressure until triethylamine hydrochloride began to precipitate. The reaction mixture was combined with water (2 L) and concentrated hydrochloric acid (2
(00 mL) with rapid stirring to give a solid. The solution was decanted from the sedimented solids; the pale yellow solid was washed with water (3 × 1 L) and decanted each time. It was filtered and washed with water (3 × 500 mL). Drying the product over P ₂ O ₅ at 50 ° C. under reduced pressure gave 562 g (88% yield) of the compound.

Compound 4 Sodium azide (52.2 g, 0.803 mol) was
Water (200 mL) was added to a 2 L three-necked flask equipped with a mechanical stirrer and reflux condenser. A gas outlet tube from the condenser was connected to a 4 L bleach (3 L) to decompose methanethiol released during the reaction.
Connected to the side arm of the filtration flask. A rubber stopper was gently placed on top of the filter and the stirred bleach was cooled in an ice bath. Compound 3 (185 g, 0.730 mol)
And isopropanol (400 mL) were added to the NaN ₃ solution and the thick slurry was stirred and slowly heated to reflux. A clear solution was obtained and the evolution of gaseous methanethiol became vigorous before reaching reflux. Heating was stopped for a few minutes to reduce the rate of methanethiol generation.

The solution was refluxed slowly for 1.5 hours, after which the pale yellow solution was cooled to room temperature. Addition of a 50% aqueous solution of NaOH (73 g, 0.91 mol) to the solution increased the solution temperature to 55 ° C. 10
After a minute, the pale orange solution was cooled to 10 ° C. Acidify the solution with concentrated hydrochloric acid (140 mL) and adjust to pH
Was set to 3. Further, 10 mL of concentrated hydrochloric acid was added, and the separated oil was extracted with dichloromethane (400 mL and 2 × 200 mL). The extracts were dried (MgSO _4), filtered, and evaporated under reduced pressure to an oil (170 g) was obtained. This oil was dissolved in acetone (450 mL) and cooled to 20 ° C. in an ice bath. Cyclohexylamine (145
g, 1.46 mol) with stirring and a precipitate formed immediately. After cooling for 30 minutes, the solid was filtered and washed with acetone to give biscyclohexylamine salt (4) (2
09g, 66%), mp 205 ° C (decomposition).

Compound 5 Compound 4 (265 g, 0.612 mol) was placed in a 1 L Erlenmeyer flask, and water (125 mL) was added. Add concentrated hydrochloric acid (125 mL) to the slurry with manual stirring
Was added in three portions. There was no fever. The thick slurry was extracted with ethyl acetate (2 × 500 mL and 5 × 200 mL). Extract the ethyl acetate with 6N hydrochloric acid (2 × 25 m
L) and brine (25 mL). The extract was dried (MgSO ₄ ), filtered and concentrated under reduced pressure to 200 mL. This solution was diluted with dichloromethane (350 mL) and then saturated with heptane. After 2 hours, the colorless solid was filtered, washed with dichloromethane and washed with P ₂ O ₅
After drying at 45 ° C. under reduced pressure, Compound 5 (105 g, 73
%), A colorless solid, mp 83-85 ° C. Concentration of the filtrate provided a second crop (24 g, 17%). Compound 6 (HT-4) Dean-Stark trap filled with Compound 5 (15.0 g, 64 mmol), n-heptanol (14.9 g, 128 mmol), and cyclohexane (75 mL) with four Angstrom molecular sieves In a flask equipped with. Toluenesulfonic acid (1.5 g) was added, the solution was slowly refluxed and the reaction continued by thin-layer chromatography (15% methanol in dichloromethane). After 2 hours, the clear, colorless solution was cooled to room temperature and diluted with ethyl acetate (200 mL). This solution was diluted with 10% sodium bicarbonate (2 × 25 m
L), washed with 3N hydrochloric acid (50 mL), water (25 mL) and brine (50 mL). The solution was finally evaporated under reduced pressure at 90 ° C. at 56.5 Torr to give a very pale yellow oil (21.8 g, theoretical yield 21.3).

[0086] (representing the coverage in g / m ²⁾ by applying a photo example A- antihalation layer the next layer a cellulose triacetate film support to prepare a bilayer photographic elements. Unless otherwise noted, all comparative and inventive compounds were dispersed twice their weight of N, N-dibutyllauramide. Layer 1 (antihalation layer): gelatin (2.04),
Black colloidal silver (0.135), UV-1 (0.
075) and UV-2 (0.075). If present, 0.0081 of the substance of the present invention and the comparative substance were added. I
0.162 of LS-1 (if present) was added. Layer 2 (cyan layer): gelatin (1.61), C-1
(0.48), C-2 (0.075), C-3 (0.0
15) and a red-sensitized AgIBr tabular emulsion (0.68
3). Layer 3 (overcoat): gelatin (5.38) and bis-vinylsulfone methyl ether (0.016).

The structure of the coupler and comparative material used (along with the corresponding ClogP) used in the above format is as follows:

Embedded image

A sample of each element is given a step exposure,
British Journal of Photography Annual, 1988,196-19
Processed by KODAK FLEXICOLOR (C41) treatment as described on page 8. Optionally, the maximum gradient between the two density points was used to measure the contrast of each element. Relative red sensitivity (a measure of speed) was determined by measuring the speed point above Dmin + 0.15 density units and normalizing to the control position. The results are shown in Table I.

[0089]

[Table 1]

Sample BL-2 shows the effect of adding a hydroquinone scavenger for an oxidized developing agent to the antihalation layer (an ordinary method for removing an undesired oxidized developing agent). However, this alternative does not have the same effect as the compounds of the present invention in reducing red Dmin. BL
-3 to BL6 demonstrate that ClogP must be sufficiently high to prevent migration of the heterocyclic thiol into the imaging layer and to prevent loss of sensitivity. While these examples achieve a reduction in Dmin, they also exhibit an undesirable decrease in relative red sensitivity. Sample BL
-7 to BL-11 indicate that the compounds of the present invention are useful for controlling the Dmin of adjacent layers without significantly affecting the sensitivity. Sample BL-
8 shows that the combination of the substance of the present invention and an oxidized developing agent scavenger is even more effective.

B-Multilayer Photographic Element The invention is more specifically described in the following multilayer experiment. Component laydown is in units of g / m ² . Layer A (protective overcoat layer) Layer B (UV filter layer) Blue sensitizing layer Layer C (yellow filter layer): ILS-1 (0.05
4) and gelatin (0.807). Green sensitizing layer Layer D (intermediate layer): ILS-1 (0.075) and gelatin (0.538). Red sensitizing layer Layer E (intermediate layer): ILS-1 (0.076) and gelatin (0.538). Layer F (Antihalation layer, AHU): Gelatin (1.
61) and UV-1 and UV-2 (both 0.07
6).

A bisvinylsulfonylmethane hardener was added at 1.55% of the total gelatin. Antifoggant (4
-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene), surfactants, coating aids, coupler solvents, emulsion additives, sequestering agents, lubricants, matting agents and coloring pigments. Add to the appropriate layer as you normally would in the art. The structure of the additional compound used in the multilayer example is shown below.

The A with and without the intermediate layer
Table II summarizes the multilayer examples ML-1-8 using all the same basic formulas with the variable part of the HU. Give a sample of each element a step exposure, British Journal of Photogr
K as described in aphy Annual, 1988, pp. 196-198
Processed by ODAK FLEXICOLOR (C41) processing.

[0094]

[Table 2]

[0095] Variations in Dmin within the multilayer film are very undesirable. The addition of an intermediate layer (Layer E) between the AHU layer and the imaging layer lowers the red Dmin, but requires an undesirable increase in film thickness and additional layers. As demonstrated by Examples ML-2 and ML-3, AHU's black colloidal silver (BCS)
Plays a major role in the cause of the increase in n. A substance such as HT-A according to the invention can be prepared using AH containing black colloidal silver.
When added to the U layer, the protective E interlayer is omitted (eg, ML
-5 and ML-6), and give low red Dmin even when present with bleach accelerator releasing couplers such as C-3.

[0096] Other preferred embodiments of the present invention are described below in connection with the claims. (Aspect 1) Elemental silver and ClogP are at least 2.0
A photographic element comprising a light-insensitive silver halide emulsion layer containing a heterocyclic thiol compound, but less than 12.0, wherein the ring system of the compound is -N = CSH
A photographic element containing a group or a tautomer thereof and which does not react with the oxidized developing agent. (Embodiment 2) The color photographic element according to embodiment 1, wherein the heterocyclic thiol is mercaptotetrazole. (Embodiment 3) The color photographic element according to embodiment 1, wherein the heterocyclic thiol is mercaptooxadiazole.

(Embodiment 4) The color photographic element according to embodiment 1, wherein the heterocyclic thiol is mercaptothiadiazole. (Embodiment 5) The color photographic element according to embodiment 1, wherein the ClogP of the heterocyclic thiol is at least 3.0 and less than 6.0. (Embodiment 6) The color photographic element according to embodiment 1, wherein the ClogP of the heterocyclic thiol is at least 3.5 and less than 6.0.

(Embodiment 7) Clo of the heterocyclic thiol
The color photographic element of embodiment 2, wherein the gP is at least 3.0 and less than 6.0. (Embodiment 8) The color photographic element according to embodiment 2, wherein the ClogP of the heterocyclic thiol is at least 3.5 and less than 6.0. (Embodiment 9) The color photographic element according to embodiment 1, wherein the elemental silver is colloidal silver and has a neutral color. (Embodiment 10) The color photographic element according to embodiment 1, wherein the elemental silver is colloidal silver and has a yellow color. (Embodiment 11) A color photographic element according to embodiment 1, wherein the heterocyclic thiol is selected from the following compounds:

Embedded image

(Embodiment 12) The color photographic element of embodiment 1, wherein the layer containing the heterocyclic thiol compound also contains an interlayer scavenger. (Embodiment 13) The color photographic element according to embodiment 12, wherein the intermediate layer scavenger is a hydroquinone compound.

(Embodiment 14) The color photographic element of embodiment 12, wherein the heterocyclic thiol compound is present as a dispersion in a hydrophobic organic solvent. (Aspect 15) The solvent is tricresyl phosphate,
N, N-diethyl lauramide, N, N′-dibutyl lauramide, p-dodecylphenol, dibutyl phthalate, di-n-butyl sebacate, Nn-butyl acetanilide, 9-octadecen-1-ol, trioctyl 15. The element of embodiment 14, wherein the element is selected from the group consisting of an amine and 2-ethylhexyl phosphate.

(Embodiment 16) The color photographic element according to embodiment 1, further comprising at least one bleaching accelerator releasing substance. (Embodiment 17) The color photographic element according to embodiment 6, further comprising at least one bleach accelerator releasing substance. (Embodiment 18) The color photographic element according to embodiment 9, wherein the red-sensitive image forming layer contains at least one bleaching accelerator substance.

Although the present invention has been described in detail with reference to certain preferred embodiments thereof, it will be understood that various changes and modifications can be made within the spirit and scope of the invention.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Stephen Paul Singer New York, USA 14559, Spencerport, Walnut Hill Drive 22 (72) Inventor Jay. Ramon Burgas United States, New York 14580, Webster, Clarendon Court 454

Claims (1)

[Claims] 1. A photographic element comprising a light-insensitive silver halide emulsion layer containing elemental silver and a heterocyclic thiol compound having a ClogP of at least 2.0 but less than 12.0, If the ring system of the compound is -N = C-
A photographic element containing an SH group or a tautomer thereof and not reacting with an oxidized developing agent.